Crosslinked hetercyclic cellulosic products

ABSTRACT

FIBROUS CELLULOSIC MATERIAL IS REACTED WITH SOLUTIONS CONTAINING A HALO-SUBSTITUTED HETEROCYCLIC (FURAN AND THIOPHENE) ACID CHLORIDE AND 1,3-BIS(4-PYRIDYL) PROPANE. CROSS-LINKKING IS EFFECTED BY REACTION BETWEEN THE CELLULOSE HALO-ESTERGROUPS FORMED AND THE PROPANE.

United States Patent 3,719,449 CROSSLINKED HETEROCYCLIC CELLULOSIC PRODUCTS Jett C. Arthur, Jr., Metairie, La., Sujan Singh, Varanasi,

India, and Ricardo H. Wade, New Orleans, La., assiguors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Apr. 27, 1972, Ser. No. 248,181 Int. Cl. D06m 13/20, 13/22, 13/34 US. Cl. 8--120 7 Claims ABSTRACT OF THE DISCLOSURE Fibrous cellulosic material is reacted with solutions containing a halo-substituted heterocyclic (furan and thiophene) acid chloride and 1,3-bis(4-pyridyl) propane. Cross-linking is effected by reaction between the cellulose halo-ester groups formed and the propane.

A non-exclusive, irrevocable, royalty-free license in the invention herein described throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of Amer- 'ica.

This invention relates to a process for the preparation of cotton and other cellulosic textile products. More specifically, this invention relates to a single-bath process wherein cellulose chemically reacts through a multistep reaction to produce crosslinked heterocyclic cellulosic furoates and thenoates. The cotton fabric derivatives produced by the process of this invention have good wrinkle recovery angles and spray ratings.

The first object of this invention is to provide a process for improving wrinkle resistance of cotton and other cellulosic fabrics.

The second object of this invention is to provide new and useful cotton derivatives with water repellency.

Cotton is the most widely used textile in the world today. However, in order to add additional properties to the natural properties of cotton and to maintain cottons competitive position with the man-made textile fibers in the market place, numerous treatments and modifications have been proposed. Among the textile uses in which cotton must compete with other textiles are out-of-door uses, such as awnings or sand bags, which require rot resistance and water resistance and clothing uses which require improved wrinkle recovery from deformation.

The cellulose furoate and Z-thenoates, which could be considered as intermediates produced in the reaction of this invention, have been disclosed in Carbohydrate Research [14 (1970) 73-82 and 17 (1971) 353463] by authors Sujan Singh and lett C. Arthur, Jr. The title of the one is Synthesis and Properties of Cellulose Furoate. The title of the second paper is Synthesis and Properties of Cellulose 2-Thenoates. These compounds are represented by the chemical equations of Scheme A. The products produced by the process of the present invention are represented by the last line of the said scheme.

The instant invention defines a distinct impro'vemnt in that rot resistant heterocyclic cellulose esters of cotton, in yarn and in fabric forms, by raction with furoyl chlorides or with thenoyl chlorides and then crosslinking the derived heterocyclic cellulose esters of cotton with the difunctional chemical, 1,3-di-(4-pyridyl)propane by the sequence of reactions shown in Scheme A to yield a textile cotton product with improved rot resistance with improved wrinkle recovery angles from deformation and "ice with improved water resistance, as evidenced by increased spray ratings.

Cl Cell- 0 H \N HCl SCHEME A Generally, the reactions were conducted in N,N-dimethyl formamide at to C. The desired amount of heterocyclic acid chloride, for example, furoyl chloride or thenoyl chloride, was added. Then the cross-linking agent, 1,3-di-(4-pyridyl)propane was added, and the mixture stirred until a homogeneous solution was obtained. Predried cotton yarn or cotton fabric was added to the solution. Then the formation of heterocyclic esters of cotton cellulose and the formation of crosslinkages of 1,3-di-(4-pyridyl)propane occurred in the absence of water.

The following examples are provided to facilitate the comprehension of the invention and should not be construed as limiting the invention in any manner whatever.

EXAMPLE 1 Cotton cellulose (4 grams, 0.022 mole of glucose residue) in the form of yarn, which had been predried in air at 60 C. for 2 hours, was added to a homogeneous solution composed of N,N-dimethylformamide (200 milliliters), 5-bromo-2-furoyl chloride (0.089 mole), and 1,3- di-(4-pyridyl) propane (0.178 mole). The mixture was heated at 80 C. in absence of moisture for 16 hours. The reacted yarn was washed at 25 C. twice with N,N-dimethylformamide milliliters each time); immersed in methanol at 50 C. for 30 minutes; then kept in 10 percent potassium hydrogen carbonate solution at 25 C. for 30 minutes; (restretching to about 80-85 percent of its initial dimension before reaction); followed by washing with water and drying to equilibrium weight at 25 C. and 50 percent relative humidity. The extent of reaction was ascertained by determining the increase in weight (add-on) of these reacted yarns over those of control yarns to be 35 percent. Control cotton yarns were soluble in 0.5 M cupriethylenediamine at 25 C.; the reacted cotton yarns were insoluble in 0.5 M cupriethylenediamine at 25 C., which indicated crosslinking of the reacted cotton yarns.

3 EXAMPLE 2 The method of Example 1, except that S-bromo-Z- thenoyl chloride (0.089 mole) was used as the acid chloride. After 20 hours of reaction the extent of reaction was determined to be 31 percent add-on. Control cotton yarns were soluble in 0.5 M cupriethylenediamine at 25 (3.; the reacted cotton yarns were insoluble in 0.5 M cupriethylenediamine at 25 C., which indicated crosslinking of the reacted cotton yarns.

EXAMPLE 3 The method of Example 1, except that S-bromo-Z-thiopheneacryloyl chloride (0.089 mole) was used as the acid chloride. After 20 hours of reaction the extent of reaction was determined to be 11 percent add-on. Control cotton yarns were soluble in 0.5 M cupriethylenediamine at 25 C.; the reacted cotton yarns were insoluble in 0.5 M cupriethylenediamine at 25 C., which indicated crossliuking of the reacted cotton yarns.

EXAMPLE 4 The method of Example 1, except that cotton cellulose in the form of fabric (printcloth, 80 x 80) was used. The extent of reaction was determined to be 22 percent. The wrinkle recovery angles of control fabrics were 188 (conditioned) and 193 (wet); the wrinkle recovery angles of reacted fabrics were 242 (conditioned) and 216 (wet). This indicated crosslinking of the reacted cotton fabric. The spray rating of control fabric was zero; the spray rating of the reacted cotton fabric (the product by the process of this invention) was 50. This indicates that the cover factors of the reacted cotton fabrics were better since they were higher than those of the control cotton fabrics.

EXAMPLE 5 The method of Example 2, except that cotton cellulose in the form of fabric (printcloth, 80 x 80) was used. The extent of reaction was determined to be 20 percent. The wrinkle recovery angles of control fabrics were 167 (conditioned) and 183 (wet). The wrinkle recovery angles of reacted fabrics were 234 (conditioned) and 225 (wet). This indicated crosslinking of the reacted cotton fabric. The spray rating of control fabric was zero; the spray rating of the reacted cotton fabric (the product by the process of this invention) was 70. This indicates that the cover factors of the reacted cotton fabrics were better since they were higher than those of the control cotton fabrics.

EXAMPLE 6 The method of Example 3, except that cotton cellulose in the form of fabric (printcloth, 80 x 80) was used. The extent of reaction was determined to be 5 percent. The wrinkle recovery angles of control fabrics were 159 (con- 4 ditioned) and 135 (wet); the wrinkle recovery angles of reacted fabrics were 192 (conditioned) and 197 (wet). This indicated crosslinking of the reacted cotton fabrics. The spray rating of the untreated control fabric was zero; the spray rating of the reacted cotton fabric (the product by the process of this invention) was 50. This indi cates that the cover factors of the reacted cotton fabrics were better since they were higher than those of the control cotton fabrics.

We claim:

1. A process for imparting to cotton and other cellulosic fabrics the desirable properties of wrinkle resistance and water repellency, the process comprising:

(a) immersing a fibrous cellulosic material in a solution containing a heterocyclic acid chloride selected from the group consisting of: 5-bromo-2-furoyl chloride, 5-brom0-2-thenoyl chloride, and 5-bromo-2-thiopheneacryloyl chloride; and 1,3-di-(4-pyridyl) propane in a molar ration of about 1:2, respectively, and

(b) heating the immersed cellulosic material in the solution of (a), in the absence of moisture, to a temperature of about to C., for about 16 to 20 hours, thereby reacting the cellulosic material with the chloride reagent to form the cellulosic furoate or the Z-thenoate as an intermediate product which subsequently is converted into the crosslinked fibrous cellulose derivatives as it reacts with the propane.

2. The process of claim 1 wherein the heterocyclic acid chloride is S-bromo-Z-furoyl chloride.

3. The process of claim 1 wherein the heterocyclic acid chloride is 5-'bromo-2-thenoyl chloride.

4. The process of claim 1 wherein the heterocyclic acid chloride is 5-bromo-2-thiopheneacryloy1 chloride.

5. The crosslinked fibrous cellulose derivative produced by the process of claim 2.

6. The crosslinked fibrous cellulosic derivative produced by the process of claim 3.

7. The crosslinked fibrous cellulose derivative produced by the process of claim 4.

References Cited Singh et al., Carbohydrate Research, 14 (1970), 73-82.

Singh et al., Carbohydrate Research, 17 (1971), 353- 363.

Singh et al., Carbohydrate Research, 18 (1971), 449- 452.

GEORGE F. LESMES, Primary Examiner J. CANNON, Assistant Examiner US. Cl. X.R. 

